Functional layers comprising Ni-inclusive ternary alloys and methods of making the same

ABSTRACT

Certain example embodiments relate to Ni-inclusive ternary alloy being provided as a barrier layer for protecting an IR reflecting layer comprising silver or the like. The provision of a barrier layer comprising nickel, chromium, and/or molybdenum and/or oxides thereof may improve corrosion resistance, as well as chemical and mechanical durability. In certain examples, more than one barrier layer may be used on at least one side of the layer comprising silver. In still further examples, a Ni x Cr y Mo z -based layer may be used as the functional layer, rather than or in addition to as a barrier layer, in a coating.

This application is a Divisional of application Ser. No. 13/064,063filed Mar. 3, 2011, the disclosure of which is incorporated herein byreference. This application also incorporates by reference the entirecontents of U.S. application Ser. No. 13/064,065, entitled “BarrierLayers Comprising Ni and/or Ti, Coated Articles Including BarrierLayers, and Methods of Making the Same,” as well as U.S. applicationSer. No. 13/064,066, entitled “Coated Article Including Low-EmissivityCoating, Insulating Glass Unit Including Coated article, and/or Methodsof Making the Same.”

Certain example embodiments of this invention relate to a coated articleincluding at least one infrared (IR) reflecting layer of a material suchas silver or the like, e.g., in a low-E coating. In certain embodiments,a Ni-inclusive ternary alloy may be used as at least one layer in thecoating. In certain examples, this Ni-inclusive ternary alloy may beprovided as a barrier layer for an IR reflecting layer comprising silveror the like. In other example embodiments, the Ni-inclusive ternaryalloy includes nickel, chromium, and/or molybdenum (e.g.,Ni_(x)Cr_(y)Mo_(z), etc.). In certain example embodiments, the provisionof a layer comprising nickel, chromium, and/or molybdenum and/or oxidesthereof permits a layer to be used that has improved corrosionresistance, as well as improved chemical and mechanical durability. Incertain example embodiments, the Ni-inclusive ternary alloy may furtherinclude Ti, Cr, Nb, Zr, Mo, W, Co, and/or combinations thereof. Infurther examples, more than one barrier layer may be used on at leastone side of the layer comprising silver. A Ni-inclusive layer may beprovided adjacent a layer comprising silver, and a second metal-basedlayer may be provided adjacent the Ni-inclusive layer. In otherexamples, a third barrier layer comprising a metal oxide may be providedadjacent the second metal-based barrier layer.

Certain example embodiments of this invention also relate to using aNi_(x)Cr_(y)Mo₂-based layer as the functional layer, rather than or inaddition to as a barrier layer, in a coating. Example coated articlesherein may be used in the context of insulating glass (IG) window units,vehicle windows, or in other suitable applications such as monolithicwindow applications, laminated windows, and/or the like.

BACKGROUND AND SUMMARY OF EXAMPLE EMBODIMENTS OF THE INVENTION

Coated articles are known in the art for use in window applications suchas insulating glass (IG) window units, vehicle windows, monolithicwindows, and/or the like. In certain example instances, designers ofcoated articles often strive for a combination of high visibletransmission, low emissivity (or low emittance), and/or low sheetresistance (R_(s)). High visible transmission may permit coated articlesto be used in applications where these characteristics are desired suchas in architectural or vehicle window applications, whereaslow-emissivity (low-E), and low sheet resistance characteristics permitsuch coated articles to block significant amounts of IR radiation so asto reduce for example undesirable heating of vehicle or buildinginteriors. Thus, typically, for coatings used on architectural glass toblock significant amounts of IR radiation, high transmission in thevisible spectrum is often desired.

The IR reflecting layer(s) in low-E coatings impact the overall coating,and in some cases the IR reflecting layer(s) is the most sensitive layerin the stack. Unfortunately, IR reflecting layers comprising silver maysometimes be subject to damage from the deposition process, subsequentatmospheric, processes, heat treatment, chemical attacks, and/or becauseof harsh environments, In certain cases, a silver-based layer in a low-Ecoating may need to be protected from oxygen; from chemical attacks suchas from acidic and/or alkaline solutions, thermal oxidation, corrosion,and from damage occurring because of moisture including contaminantssuch as oxygen, chlorine, sulfur, acids and/or bases. If the IRreflecting layer(s) in the coating is/are not sufficiently protected,the durability, visible transmission, and/or other opticalcharacteristics of the coated article may suffer.

Accordingly, it will be appreciated by one skilled in the art that thethere is a need for a low-E coating with improved durability andimproved or substantially unchanged optical properties.

Certain example embodiments of this invention relate to an improvedbarrier layer material comprising an Ni-inclusive ternary alloy used inconnection with an IR reflecting layer comprising silver. In certaininstances, the improved barrier layer material may permit the durabilityof the coated article to be improved. However, other example embodimentsrelate to an IR reflecting layer comprising a Ni-inclusive ternary alloy(e.g., nickel, chromium, and/or molybdenum). In these cases, the use ofan IR reflecting layer-comprising a Ni-inclusive ternary alloy may alsoresult in a coated article having an improved chemical and/or mechanicaldurability.

Certain example embodiments of this invention relate to a method ofmaking a coated article including a coating supported by a glasssubstrate. In certain example embodiments, the method comprises:disposing a dielectric layer on the glass substrate; disposing a firstbarrier layer comprising a Ni-inclusive ternary alloy over thedielectric layer; disposing an IR reflecting layer comprising silverover the Ni-inclusive ternary alloy; and disposing a second barrierlayer comprising a Ni-inclusive ternary alloy over the IR reflectinglayer, wherein the coating is used as a low-E coating.

Other example embodiments relate to a method of making a coated article,the method comprising: disposing a dielectric layer on a glasssubstrate; disposing a first barrier layer over the dielectric layer;disposing an IR reflecting layer comprising silver over the Ni-inclusiveternary alloy; and disposing a second barrier layer over the IRreflecting layer, wherein the coating is used as a low-E coating,wherein the first and second barrier layers comprise 54-58 wt. % Ni,20-22.5 wt. % Cr, and 12.5-14.5 wt. % Mo.

Still further example embodiments relate to a coated article. In somecases, the coated article comprises a substrate supporting a low-Ecoating. The low-E coating may comprise, in order moving away from thesubstrate: a first dielectric layer; a first barrier layer; a first IRreflecting layer comprising silver, provided over and contacting thefirst barrier layer; a second barrier layer, provided over andcontacting the IR reflecting layer; and a second dielectric layerprovided over the second barrier layer, wherein the first and secondbarrier layers comprise 54-58 wt, % Ni, 20-22.5 wt. % Cr, and 12.5-14.5wt. % Mo.

Other embodiments of this invention related to a method of making acoated article including a coating supported by a glass substrate, themethod comprising: disposing a dielectric layer on the substrate;disposing a first sub-barrier layer comprising one or more of Nb, Ti,Cr, and Zr over the dielectric layer; disposing a first barrier layercomprising a Ni-inclusive alloy over and contacting the firstsub-barrier layer; disposing an IR reflecting layer comprising silverover and contacting the first barrier layer comprising an Ni-inclusivealloy; disposing a second barrier layer comprising a Ni-inclusive alloyover and contacting the IR reflecting layer; and disposing a secondsub-barrier layer comprising one or more of Nb, Ti, Cr, and Zr over andcontacting the Ni-inclusive barrier layer.

Still further example embodiments also relate to a method of making acoated article including a coating supported by a glass substrate. Insome cases, the method comprises: disposing a dielectric layer on thesubstrate; disposing a first sub-barrier layer comprising one or more ofNb, Ti, Cr, and Zr over the dielectric layer; disposing a first barrierlayer comprising Ni, Cr, Ti, and/or Mo over and contacting the firstsub-barrier layer; disposing an IR reflecting layer comprising silverover and contacting the first barrier layer comprising Ni, Cr, Ti,and/or Mo; disposing a second barrier layer comprising Ni, Cr, Ti,and/or Mo over and contacting the IR reflecting layer; and disposing asecond sub-barrier layer comprising one or more of Nb, Ti, Cr, and Zrover and contacting the layer comprising Ni, Cr, Ti, and/or Mo.

Other example embodiments relate to a method of making a coated article,the method comprising: disposing a dielectric layer on a glasssubstrate; disposing a first barrier layer over the dielectric layer;disposing an IR reflecting layer comprising silver over and contactingthe first barrier layer; disposing a second barrier layer comprisingNiTi or an oxide thereof over and contacting the IR reflecting layer;disposing a third barrier layer comprising NiCr or an oxide thereof overand contacting the second barrier layer; and disposing a fourth barrierlayer comprising an oxide of Sn, Ti, Cr, Nb, Zr, Mo, W, and/or Co overand contacting the third barrier layer.

Additional example embodiments relate to a coated article. The coatedarticle comprises a low-E coating. The coating comprises: a glasssubstrate; a dielectric layer; a first sub-barrier layer comprising oneor more of Nb, Ti, Cr, and Zr over the dielectric layer; a first barrierlayer comprising Ni, Cr, Ti, and/or Mo over and contacting the firstsub-barrier layer; an IR reflecting layer comprising silver over andcontacting the first barrier layer comprising Ni, Cr, Ti, and/or Mo; asecond barrier layer comprising Ni, Cr, Ti, and/or Mo over andcontacting the IR reflecting layer; and a second sub-barrier layercomprising one or more of Nb, Ti, Cr, and Zr over and contacting thelayer comprising Ni, Cr, Ti, and/or Mo.

Still another example embodiment of this invention relates to a methodof making a coated article comprising a coating supported by a glasssubstrate, the method comprising: disposing a first dielectric layer onthe substrate; disposing an IR reflecting layer comprising 54-58 wt. %Ni, 20-22.5 wt. % Cr, and 12.5-14.5 wt. % Mo over and contacting thefirst dielectric layer; and disposing a second dielectric layer over andcontacting the IR reflecting layer.

Other examples relate to method of making a coated article comprising acoating supported by a glass substrate, the method comprising: disposinga first dielectric layer comprising silicon nitride on the substrate;disposing an IR reflecting layer comprising 54-58 wt. % Ni, 20-22.5 wt.% Cr, and 12.5-14.5 wt. % Mo over and contacting the first dielectriclayer; disposing a barrier layer comprising NbZr over and contacting theIR reflecting layer; disposing a second dielectric layer comprisingsilicon nitride over and contacting the IR reflecting layer; anddisposing an overcoat layer comprising an oxide of zirconium over andcontacting the second dielectric layer.

Example embodiments of this invention also relate to a coated articlecomprising: a glass substrate; a first dielectric layer comprisingsilicon nitride on the substrate; an IR reflecting layer comprising54-58 wt. % Ni, 20-22.5 wt. % Cr, and 12.5-14.5 wt. % Mo over andcontacting the first dielectric layer; a barrier layer comprising NbZrover and contacting the IR reflecting layer; a second dielectric layercomprising silicon nitride over and contacting the IR reflecting layer;and an overcoat layer comprising an oxide of zirconium over andcontacting the second dielectric layer.

Certain example embodiments also relate to coated articles and/or IGunits made by one of the above-described and/or other methods.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional view of a coated article comprising a singleIR reflecting layer and Ni-inclusive ternary alloy barrier layersaccording to an example embodiment of this invention.

FIGS. 2( a)-(b) are cross-sectional views of coated articles comprisinga single IR reflecting layer and Ni_(x)Cr_(y)Mo_(x)-based barrier layersaccording to an example embodiment of this invention.

FIGS. 3( a)-(c) are cross-sectional views of coated articles comprisinga single IR reflecting layer and barrier layers based on NiCrMo, NiTiand/or NiCr according to an example embodiment of this invention.

FIG. 4 is a cross-sectional view of a coated article comprising at leasttwo IR reflecting layers and Ni-inclusive ternary alloy barrier layersaccording to an example embodiment of this invention.

FIG. 5 is a cross-sectional view of a coated article comprising a atleast two IR reflecting layers and Hastelloy-based barrier layersaccording to an example embodiment of this invention

FIG. 6 is a cross-sectional view of a coated article comprising an IRreflecting layer, and first and second barrier layers provided on eachside of the IR reflecting layer according to still another exampleembodiment of this invention.

FIG. 7 is a cross-sectional view of a coated article comprising an IRreflecting layer, and first Ni-inclusive barrier layers adjacent the IRreflecting layer, and second metal-based barrier layers adjacent to thefirst barrier layers, according to still another example embodiment ofthis invention.

FIG. 8 is a cross-sectional view of a coated article comprising an IRreflecting layer, and first C22-based barrier layers adjacent the IRreflecting layer, and second NbZr-based barrier layers adjacent to thefirst barrier layers, according to still another example embodiment ofthis invention.

FIG. 9 is a cross-sectional view of a coated article comprising at leasttwo IR reflecting layers, and first Ni-inclusive barrier layers adjacentthe IR reflecting layers, and second metal-based barrier layers adjacentto the first barrier layers, according to still another exampleembodiment of this invention.

FIG. 10 is a cross-sectional view of a coated article comprising an IRreflecting layer, and first and second barrier layers provided on eachside of the IR reflecting layer, wherein the barrier layers closest toand farthest from the glass substrate are sandwiched in between twodielectric layers, according to still another example embodiment of thisinvention.

FIG. 11 is a cross-sectional view of a coated article comprising atleast two IR reflecting layers, and first and second barrier layersprovided on each side of each IR reflecting layer, wherein the barrierlayers closest to and farthest from the glass substrate are sandwichedin between two dielectric layers, according to still another exampleembodiment of this invention.

FIG. 12 is a cross-sectional view of a coated article comprising an IRreflecting layer, and a first NiTi-based barrier layer, a secondNiCr-based barrier layer, and a third metal oxide-based barrier layer,according to still another example embodiment of this invention.

FIG. 13 is a cross-sectional view of a coated article comprising atleast two IR reflecting layers, and a first NiTi-based barrier layer, asecond NiCr-based barrier layer, and a third metal oxide-based barrierlayer, according to still another example embodiment of this invention.

FIG. 14 is a cross-sectional view of a coated article comprising aNiCrMo-based functional layer, according to still further exampleembodiments of this invention.

FIG. 15 is a cross-sectional view of a coated article comprising aC22-based functional layer sandwiched between two silicon nitride-baseddielectric layers, with a zirconium oxide based overcoat, according toyet another example embodiment of this invention.

FIG. 16 is a cross-sectional view of a coated article comprising aC22-based functional layer and an NbZr-based barrier layer, sandwichedbetween dielectric layers with a zirconium oxide-based overcoat,according to still further example embodiments of this invention.

DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS OF THE INVENTION

Referring now to the drawings in which like reference numerals indicatelike parts throughout the several views.

Coated articles herein may be used in coated article applications suchas monolithic windows, IG window units, vehicle windows, and/or anyother suitable application that includes single or multiple substratessuch as glass substrates.

As indicated above, in certain cases, IR reflecting layers (e.g., asilver-based layer) in a low-E coating may need to be protected fromdamage arising from subsequent deposition processes, thermal oxidation,corrosion, moisture, chemical attacks, and/or harsh environments. Forexample, the oxygen in the plasma used to deposit subsequent layers maybe highly ionized and the silver-based layer may need to be protectedfrom it. Also, in post-deposition “atmospheric processes,” thesilver-based layer may be susceptible to attacks from oxygen, moisture,acids, bases, and/or the like. This may be particularly true if a layerlocated between the silver-based layer and the atmosphere has anydefects, such that the silver-based layer is not covered entirely (e.g.,scratches, pin holes, etc.).

For example, degradation of coatings including layers comprising silvermay also be caused by a physical restructuring of the Ag in the layerand its resulting disruption of overlying layers upon heating, incertain instances. Problems may arise during heat-treating in certainexample embodiments. In those cases, oxygen may diffuse into thesilver-based layer. In certain example embodiments, oxygen that reachesthe silver-based layer may affect its properties, such as by decreasingsheet resistance, affecting emissivity, and/or producing haze, etc., andmay result in reduced performance by the layer stack. In other cases. Agagglomeration may cause defects.

In certain example embodiments, barrier layers may therefore be usedwith silver-based layers (and/or other IR reflecting layers) in low-Ecoatings in order to reduce the occurrence of some or all of theabove-described and/or other issues. In certain exemplary cases, thesebarrier layers may form a thin protective oxide layer around the silver,and improve the corrosion resistance, chemical, and/or mechanicaldurability of the coated article.

Certain embodiments of this invention relate to a coated article thatincludes at least one glass substrate supporting a coating. The coatingtypically has at least one infrared (IR) reflecting layer that reflectsand/or blocks at least some IR radiation. The IR reflecting layer(s) maybe of or include a material such as silver, gold, NiCr, and/or ternaryalloys thereof, or the like, in different embodiments of this invention.Often, an IR reflecting layer is sandwiched between at least first andsecond contact layers of the coating.

In view of the foregoing, it would be advantageous to provide a barrierlayer comprising a Ni-inclusive ternary alloy. In certain examples, thebarrier layer may comprise material(s) such as nickel, chromium, and/ormolybdenum (e.g., Haynes alloys such as C22, BC1, and/or B3). In otherexample embodiments, the Ni-inclusive ternary alloy may further includeTi, Cr, Nb, Zr, Mo, W, Co and/or combinations thereof. In certaininstances, a Ni-inclusive ternary alloy barrier layer (e.g., comprisingmaterials such as nickel, chromium, and/or molybdenum, etc.) may have(1) sufficient adhesion to the IR reflecting layer; (2) improvedcorrosion resistance to acidic and/or alkaline solutions; (3) protectionduring high temperature oxidation; and (4) improved overall chemicaland/or mechanical durability. In other example embodiments, theseadvantages may arise from using a layer comprising nickel, chromium,and/or molybdenum as an IR reflecting layer and/or other functionallayer, rather than as a barrier layer.

Furthermore, in other example embodiments, more than one barrier layermay be provided. It has advantageously been found that the provision ofat least two barrier layers on at least one side of the IR reflectinglayer (and in some cases both sides) may result in the aforesaidadvantages, in certain example embodiments, a Ni-inclusive alloy orNi-inclusive ternary alloy may be used adjacent to an IR reflectinglayer, and a material providing good corrosion resistances, and goodchemical and mechanical durability may be chosen as the second barrierlayer.

FIG. 1 is a cross-sectional view of a coated article according to anexample embodiment of this invention. In certain example embodiments,the coated article illustrated in FIG. 1 may be used as a monolithicwindow with a low-E coating on surface 1 and/or 2, where the low-Ecoating includes only a single IR reflecting layer. However, in otherexample embodiments, the coated article in FIG. 1 may comprise furtherlayers. Furthermore, a coated article made according to exampleembodiments described herein may be used in an insulated glass unit(IGU), with the coating(s) on surface 1, 2, 3, and/or 4; in a laminatedmonolithic lite with the coating embedded against the interlayer onsurfaces 2 and/or 3, or exposed on surface 1 or 4; in a laminated IGU,with a laminate outboard with the coating embedded against theinterlayer on surfaces 2 and/or 3, or exposed on surface 4 or elsewhere;in a laminated IGU, with a laminated inboard with the coated exposed onsurfaces 3 and/or 6, or embedded on surfaces 4 and/or 5, according todifferent example embodiments and applications. In other words, thiscoating may be used monolithically, or in IG units comprising two ormore substrates, or more than once in a glass unit, and may be providedon any surface of the unit in different example embodiments.

The coated article includes glass substrate 1 (e.g., clear, green,bronze, or blue-green glass substrate from about 1.0 to 10.0 mm thick,more preferably from about 1.0 mm to 6.0 mm thick), and a multi-layercoating 35 (or layer system) provided on the substrate either directlyor indirectly.

As shown in FIG. 1, the coating 35 comprises optional dielectriclayer(s) 3 and/or 5, first barrier layer 7 comprising a Ni-inclusiveternary alloy, which may be of or include Ni, Ti, Cr, Nb, Zr, Mo, W, Coand/or combinations thereof (e.g., Ni_(x)Cr_(y)Mo_(z),Ni_(x)Ti_(y)Cr_(z), Ni_(x)Ti_(y)Nb_(z), Ni_(x)Nb_(y)Zr_(z),Ni_(x)Cr_(y)Zr_(z), Ni_(x)Ti_(y)Mo_(z), Ni_(x)Zr_(y)Mo_(z),Ni_(x)Nb_(y)Mo_(z), Ni_(x)Cr_(y)Mo_(z), Ni_(x)W_(y)Cr_(z),Ni_(x)W_(y)Mo_(z), Ni_(x)W_(y)Zr_(z), Ni_(x)Co_(y)Mo_(z),Ni_(x)Co_(y)Xr_(z); Ni_(x)Co_(y)Zr_(z), Ni_(x)Co_(y)Nb_(z), and/orNi_(x)Co_(y)Ti_(z)), IR reflecting layer 9 including one or more ofsilver, gold, or the like, second barrier layer 11 comprising aNi-inclusive ternary alloy, which may be of or include Ni, Ti, Cr, Nb,Zr, Mo, W, Co and/or combinations thereof (e.g., Ni_(x)Cr_(y)Mo_(z);Ni_(x)Ti_(y)Cr_(z), Ni_(x)Ti_(y)Nb_(z), Ni_(x)Nb_(y)Zr_(z),Ni_(x)Cr_(z)Zr_(z), Ni_(x)Ti_(y)Mo_(z), Ni_(x)Zr_(y)Mo_(z),Ni_(x)Nb_(y)Mo_(z), Ni_(x)Cr_(y)Mo_(z), Ni_(x)W_(y)Cr_(z),Ni_(x)W_(y)Mo_(z), Ni_(x)W_(y)Zr_(z), Ni_(x)W_(y)Nb_(z),Ni_(x)W_(y)Ti_(z), Ni_(x)Co_(y)Mo_(z), Ni_(x)Co_(y)Cr_(z),Ni_(x)Co_(y)Mo_(z), Ni_(x)Co_(y)Zr_(z), Ni_(x)Co_(y)Nb_(z), and/orNi_(x)Co_(y)Ti_(z)), and optional dielectric layer(s) 13, that may incertain example instances be a protective overcoat. Other layers and/ormaterials may also be provided in certain example embodiments of thisinvention, and it is also possible that certain layers may be removed orsplit in certain example instances. Layers 3, 5, and/or 13 may includeone or more discrete layers. Dielectric layers 3, 5, and 13 may be of orinclude silicon nitride, silicon oxide, silicon oxynitride, tin oxide,titanium oxide, and/or any suitable dielectric material. Optionalovercoat layer 16 may be provided in certain example embodiments. Inother examples, it may be excluded. In certain example embodiments, whenoptional overcoat layer 16 is provided, layer 16 may be of or includezirconium. The zirconium-based layer may be oxided partially or fully indifferent examples. In further example embodiments, layer 16 maycomprise an oxide of a zirconium-based alloy, such as Zr_(x)Mo_(y)O_(z),ZrAiOx, and/or TiZrOx. These materials may advantageously contribute tobetter tribological and/or frictional properties of the coating and/orcoated article. Other dielectric layers may be provided in other placesin the coating in other examples. In certain example embodiments, thelayer may be at least initially deposited as a nitride of zirconium.

Infrared (IR) reflecting layer 9 is preferably substantially or entirelymetallic and/or conductive, and may comprise or consist essentially ofsilver (Ag), gold, or any other suitable IR reflecting material. IRreflecting layer 9 helps allow the coating to have low-E and/or goodsolar control characteristics such as low emittance, low sheetresistance, and so forth. The IR reflecting layer 9 may, however, beslightly oxidized in certain embodiments of this invention.

The IR reflecting layers shown in FIG. 1 and described herein maycomprise or consist essentially of silver in different exampleembodiments. Thus, it will be appreciated that certain exampleembodiments may include silver alloys. In such cases. Ag may be alloyedwith an appropriate amount of Zr, Ti, Ni, Cr, Pd, and/or combinationsthereon. In certain example embodiments. Ag may be alloyed with both Pdand Cu, with approximately 0.5-2% (by weight or atomic %) of each of Pdand Cu, Other potential alloys include Ag and one or more of Co, C, Mg,Ta, W, NiMg, PdGa, CoW, Si, Ge, Au, Pt, Ru, Sn, Al, Mn, V, In, Zn, Ir,Rh, and/or Mo. In general, dopant concentrations may be in the range of0.2-5% (by weight or atomic %), more preferably between 0.2-2.5%.Operating within these ranges may help the silver maintain the desirableoptical characteristics of the Ag-based layer that otherwise might belost by virtue of the alloying, thereby helping to maintain the overalloptical characteristics of the stack while also enhancing chemical,corrosion, and/or mechanical durability. The example Ag alloy targetmaterials identified herein may be sputtered using a single target,deposited by co-sputtering using two (or more targets), etc. In additionto providing improved corrosion resistance, the use of Ag alloys may incertain instances help to reduce the silver diffusivity at elevatedtemperatures while also helping to reduce or block the amount of oxygenmovement in the layer stacks. This may further enhance silverdiffusivity and may change those Ag growth and structural propertiesthat potentially lead to had durability.

In certain example embodiments, barrier layer 7 may be of or include anoxide of zinc. It will be appreciated that the first and secondNi-inclusive ternary alloy layers 7 and 11 may have the same ordifferent compositions in different embodiments of this invention.

Dielectric layer 13 may be of or include silicon nitride, silicon oxide,silicon oxynitride, tin oxide, titanium oxide, and the like, Dielectriclayer 13 may comprise more than one discrete layer in certain exampleembodiments. Furthermore, dielectric layer 13 may serve as a protectiveovercoat in some cases.

It has advantageously been found that the use of, for example, aNi-inclusive ternary alloy in these layers allows improved corrosionresistance, and better chemical and/or mechanical durability. It isbelieved that the use of a Ni-inclusive ternary alloy (and or an oxide,nitride, and/or oxynitride thereof) forms a protective layer on thegrain boundaries of Ag. This may result in a coated article with bettercorrosion and/or moisture resistance, and chemical durability, incertain example embodiments. Furthermore, it is believed that oxygendiffusion may be reduced because of the formation of thin protectiveoxide layers around the IR reflecting layer, which may also help improvecorrosion resistance, chemical, and mechanical durability in certainexample embodiments.

In certain exemplary embodiments, the Ni-inclusive ternary alloy maycomprise nickel, chromium, and/or molybdenum, Nickel and Ni-inclusivealloys may be able to withstand a variety of corrosive environments,high temperatures, high stress, and/or a combination of these factors,in certain example embodiments. However, in some cases, Ni may providegood corrosion resistance in normal environments, but may be sensitiveto high temperature moisture and/or acid attacks. Thus, Cr may be addedto provide improved corrosion resistance to acidic solutions in certainexamples. Cr may also provide protection from high temperature oxidationin other examples.

However, a barrier layer consisting of, or consisting essentially of, Niand/or Cr may still be improved. For example, a layer consistingessentially of NiCr as-deposited, and heated in air (which may then forman oxide of NiCr), may experience corrosion and/or etching whensubjected to hot acidic and alkaline solutions. An NiCr heated coatingmay be etched away in (1) 20% NaOH (65 degrees C.; 1 hr); (2) 50% H2SO4(65 degrees C.; 1 hr) and in (3) 5% HCl (65 degrees C.; 1 hr).Furthermore, when subjected to boiling water (100 degrees C.; 1 hr),heated NiCr has been observed to become hazy. This may be because of theformation of chlorides and/or hydrides.

As another example, a NiCr-inclusive layer as-coated (e.g., partiallyoxidized or less oxided than a heated NiCr-inclusive layer) may beetched away by 50% H₂SO₄ (65 degrees C.; 1 hr) and 5% HCl (65 degreesC.; 1 hr). Therefore, it can be seen that an IR reflecting layer (e.g.,comprising silver) may be vulnerable to chemical attacks and/or in harshenvironments (e.g., in hot and/or humid environments). Therefore, thereis a need for an improved barrier layer. This may be particularly truefor applications wherein the coated article will be used monolithicallyor on an outer surface of an IG unit or laminated assembly, because thecoating may be exposed to the elements in certain example embodiments.

Thus, in monolithic applications where a coating is provided, in IGunits where coatings are provided on surfaces 1 (e.g., foranti-condensation) and/or 4 (e.g., for improving U-value), and othercases where these coatings may be exposed directly to the environment,it may be desirable to use these materials with better corrosionresistance, and improved chemical and/or mechanical durability, e.g.,for protection of Ag-based layers.

It has been found that molybdenum, particularly when used with nickel,may improve resistance to acids, as well as to pitting and crevicecorrosion, in certain example embodiments. Furthermore, molybdenum,particularly when used with chromium, may provide improved propertieswith respect to corrosion from alkaline solutions. Therefore, it hasadvantageously been found that the use of NiCrMo-based alloyssurrounding a silver-based layer may provide improved corrosionresistance, and improved chemical and/or mechanical durability in low-Estacks. NiCrMo-based barriers, both as-deposited and heat treated, mayprovide a coating with improved performance as compared to barrierlayers consisting and/or consisting essentially of Ni and Cr.

It has advantageously been found that NiCrMo-based alloys (e.g. C22,BC1, and/or B3 Hallestoy) may protect a coating including at least onesilver-based layer better than layers consisting essentially of Ni andCr in some cases. Furthermore, NiCrMo-based alloys may protect thecoated article from visible damage in further examples. It is furtherbelieved that NiCrMo may form an alloy with the top dielectric layer(e.g., layer 13) in the coating, which may also even improve theperformance of this layer against alkaline solutions and boiling water.This may be particularly true in embodiments where the top dielectriclayer 13 is silicon based. For example, materials comprising MoSi areused as heaters at higher temperatures because of their good thermal andcorrosion resistance.

Tables 1-3 show the compositions of three example embodiments ofNiCrMo-based alloys (e.g., C22, BC1, and B3) for reference.

TABLE 1 First Example Embodiment of Ni_(x)Cr_(y)Mo_(z) (e.g., C22) -elemental composition by wt. % Element Preferred More Preferred ExampleNi 40-70% 50-60% 54-58% (e.g., 56%) Cr  5-40% 10-30% 20-22.5% Mo  5-30%10-20% 12.5-14.5% Fe  0-15%  0-10% 1-5% (e.g., 3%) W  0-15%  0-10% 1-5%(e.g., 3%) Co  0-15%  0-10% 1-5% (e.g., 3%) Si  0-2%  0-1% =<0.2% (e.g.,.08%) Mn  0-3%  0-2% =<1% (e.g., 0.5%) C  0-1%  0-0.5%  =<0.1% (e.g.,.01%) V  0-2%  0-1% =<1% (e.g., 0.35%) Al — — — Ti — — —

TABLE 2 Second Example Embodiment of Ni_(x)Cr_(y)Mo_(z) (e.g., B3) -elemental composition by wt. % Element Preferred More Preferred ExampleNi 50-80% 60-70% 63-67% (e.g., 65%) Cr  0-15%  0-5% 1-2% (e.g., 1.5%) Mo10-50% 20-40% 25-30% (e.g., 28.5%) Fe  0-10%  0-5% 1-4% (e.g., 3%) W 0-15%  0-10% 1-5% (e.g., 3%) Co  0-15%  0-10% 1-5% (e.g., 3%) Si  0-2% 0-1% =<0.2% (e.g., .1%) Mn  0-15%  0-10% 1-5% (e.g., 3%) C  0-1% 0-0.5%  =<0.1% (e.g., .01%) V — — — Al  0-3%  0-2% =<1% (e.g., 0.5%) Ti 0-2%  0-1% =<0.5% (e.g., .2%)

TABLE 3 Third Example Embodiment of Ni_(x)Cr_(y)Mo_(z) (e.g., BC1) -elemental composition by wt. % Element Preferred More Preferred ExampleNi 50-80% 60-70% 60-65% (e.g., 62%) Cr  5-30% 10-20% 12-17% (e.g., 15%)Mo 10-40% 15-25% 20-25% (e.g., 22%) Fe  0-10%  0-5% 1-3% (e.g., 2%) W —— — Co — — — Si  0-2%  0-1% =<0.2% (e.g., .08%) Mn  0-5%  0-2% =<0.5%(e.g., 0.25%) C  0-1%  0-0.5%  =<0.1% (e.g., 0.01%) V — — — Al  0-3% 0-2% =<1% (e.g., 0.5%) Ti — — —

FIG. 2( a) includes coating 35′. FIG. 2( a) is based on FIG. 1, exceptFIG. 2( a) specifically calls for layers 7 and 11 to comprise an alloycomprising NiCrMo. In certain example embodiments, layers 7 and/or 11may further comprise Fe, W, Co, Si, Mn, C, V, Al, and/or Ti, inpotentially small amounts, e.g., as indicated above in Table 1.

FIG. 2( b) illustrates coating 35″. FIG. 2( b) is based on FIGS. 1 and2( a), except FIG. 2( b) specifically calls for layers 7 and 11 to be ofor include Hastelloy C22 and specifies that the optional overcoatincludes Zr.

FIG. 3( a) illustrates a different example embodiment. In the FIG. 3( a)embodiment, different Ni-based alloys may advantageously be used withinone coating 36 in order to further improve the properties of thecoating. In example embodiments related to FIGS. 3( a)-(c), the Ni-basedalloy is not necessarily ternary. In some cases, the Ni-based alloy maybe binary, or may comprise more than 3 metals. For instance, layer 7 maybe of or include NiCr (and/or an oxide and/or nitride thereof), whilelayer 11 is of or includes NiTi (and/or an oxide and/or nitridethereof). In certain example embodiments, a layer stack wherein layer 7is NiCr-based and layer 11 is NiTi-based, the sheet resistance may befrom about 25 to 45% lower than that of a layer stack where layers 7 and11 are both NiCr-based; more preferably from about 30 to 40% lower, andmost preferably at least 34% lower.

As another example, layer 7 may be of or include NiCr (and/or an oxideand/or nitride thereof), while layer 11 is of or includesNi_(x)Cr_(y)Mo_(z) (e.g., C22). In certain example embodiments, a layerstack wherein layer 7 is NiCr-based and layer 11 isNi_(x)Cr_(y)Mo_(z)-based, the sheet resistance may be from about 20 to35% lower than that of a layer stack where layers 7 and 11 are bothNiCr-based more preferably from about 25 to 30% lower, and mostpreferably at least 28% lower.

Thus, in certain exemplary embodiments, layer 7 may be of or include atleast one of NiCr, Ni_(x)Cr_(y)Mo_(z) (e.g., C22, B3, BC1, etc.), andNiTi, and layer 11 may also be of or include at least one of NiCr,Ni_(x)Cr_(y)Mo_(z) (e.g., C22, B3, BC1, etc.), and NiTi, so long as thematerial chosen for layer 7 is different from the material chosen forlayer 11.

FIG. 3( b) shows a coated article 1 supporting coating 36′. FIG. 3( b)is based on FIG. 3( a), except FIG. 3( b) specifically calls for layer 7to be of or include NiCr (and/or an oxide and/or nitride thereof), andfor layer 11 to be of or include NiTi (and/or an oxide and/or nitridethereof).

FIG. 3( c) shows a coated article 1 supporting coating 36″. FIG. 3( c)is based on FIG. 3( a), except FIG. 3( c) specifically calls for layer 7to be of or include NiCr (and/or an oxide and/or nitride thereof), andfor layer 11 to be of or include Ni_(x)Cr_(y)Mo_(z) (and/or an oxideand/or nitride thereof).

As discussed above, coatings made according to FIG. 3( a)-(c) mayadvantageously have a sheet resistance that is significantly reduced,e.g., as compared to a coating including only NiCr-based barrier layers.

FIG. 4 is a cross-sectional view of a coated article according to anexample embodiment of this invention. In certain exampleimplementations, the coated article illustrated in FIG. 4 may be used asa monolithic window with a low-E coating with two IR reflecting layers.The coated article includes glass substrate 1 (e.g., clear, green,bronze, or blue-green glass substrate from about 1.0 to 10.0 mm thick,more preferably from about 1.0 mm to 6.0 mm thick), and a multi-layercoating (or layer system) 45 provided on the substrate either directlyor indirectly. The FIG. 4 embodiment includes glass substrate 1,dielectric layer(s) 3 and/or 5, Ni-inclusive ternary alloy 7,silver-based layer 9, Ni-inclusive ternary alloy 11, silver-based layer19, Ni-inclusive ternary alloy 21, dielectric layer(s) 13 and optionalovercoat layer 16. Layers 7, 11, and/or 21 may be of or include anyand/or all of the example materials discussed herein with respect tolayer 7 in the FIG. 1 example embodiment. Similarly, the Ag-based layers9 and 19 may be silver alloys as discussed herein. Dielectric layers 3,5, 13, and 16 are optional. These layers may comprise any of thematerials discussed for these layers herein. Some, all, or none of theselayers may be provided according to different example embodiments.

FIG. 5 is based on FIG. 4, and includes coating 45′. FIG. 5 specifiesthat layers 7, 9, 11 and/or 19 may comprise NiCrMo-based alloys (e.g.,C22, BC1, and/or B3).

Other example embodiments, such as that shown in FIG. 6, relate toanother aspect of certain example embodiments of this invention alludedto above. In these example embodiments, it has been found that theprovision of two barrier layers on each or either side of a functionallayer (e.g., an IR reflecting layer comprising silver) may result inimproved durability.

More particularly, FIG. 6 is a cross-sectional view of a coated articleaccording to an example embodiment of this invention. The coated articleincludes glass substrate 1 (e.g., clear, green, bronze, or blue-greenglass substrate from about 1.0 to 10.0 mm thick, more preferably fromabout 1.0 mm to 6.0 mm thick), and a multi-layer coating 50 (or layersystem) provided on the substrate either directly or indirectly. Coating50 is supported by the glass substrate 1 and includes optionaldielectric layer(s) 3 and/or 5, first and second barrier layers 8/10 and6/12 sandwiching silver-based layer 9, dielectric layer(s) 13, andoptional overcoat layer 16.

Optional dielectric layer(s) 3, 5, and 13 may be of or include siliconnitride, silicon oxide, silicon oxynitride, titanium oxide, tin oxide,and any other suitable dielectric material. All, none, or some of theselayers may be present according to different example embodiments. Infurther example embodiments, each of these layers may include one ormore discrete layers.

Optional overcoat layer 16 may be provided in certain exampleembodiments. In other examples, it may be excluded. In certain exampleembodiments, when optional overcoat layer 16 is provided, layer 16 maybe of or include zirconium. The zirconium-based layer may be oxidedpartially and/or fully in certain cases. In further example embodiments,layer 16 may comprise an oxide of a zirconium-based alloy, such asZr_(x)Mo_(y)O_(z), ZrAlOx and/or TiZrOx. These materials mayadvantageously contribute to better tribological and/or frictionalproperties of the coating and/or coated article.

Still referring to FIG. 6, barrier layers 6 and 12 may comprise, amaterial selected for improved corrosion resistance and/or enhancedchemical and mechanical durability. The adhesion between the “barrier 1”layers 8 and 10 (discussed in detail below) and “barrier 2” layers 6 and12 is advantageous in certain example embodiments. In certain instances,layers 6 and 12 may adhere well to layers 8 and 10 respectively, as wellas to dielectric layer 12. Furthermore, the materials for layers 6 and12 may be chemically compatible with the materials used for layers 8 and10 in certain embodiments.

For heat treatable (e.g., temperable) coatings, it may be desirable incertain instances that the materials used for layers 6 and 12 bethermally stable. It also may be desirable in certain example instancesthat these materials not significantly optically or physically degradethe performance of the coating following heat treatment.

In view of the foregoing, it has advantageously been found that “barrier2” layers 6 and 12 may comprise Nb, Zr, Ti, Cr, and/or Nb. For instance,layers 6 and/or 12 may comprise NbZr, Zr, TiCr, and/or TiNb. Thesematerials provide good corrosion and chemical resistance properties forannealed and/or heat treatable coatings in certain example embodiments.In certain example embodiments, TiCr may be used as “barrier 2” when thecoating is annealed. In other example embodiments, Zr, NbZr, and/or TiNbmay be used for layers 6 and/or 12 when the coating is heat-treated.

Still referring to the FIG. 6 embodiment, a Ni-inclusive alloy may beused adjacent to the layer 9 comprising silver. In certain exampleembodiments, “barrier 1” (layers 8 and 10), the barrier layer closest tothe layer comprising silver, may be of or include Ni. Layers 8 and/or 10may further include one or more of Cr, Mo, and/or Ti. NiCrMo, NiCr,and/or NiTi may be used for layers 8 and/or 10 in certain exemplaryembodiments. It has advantageously been found that the use of thesematerials for layers 8 and/or 10, near or adjacent to the silver-basedlayer, may provide better adhesion and chemical compatibility with thelayer comprising Ag. In certain example embodiments, Ti alone may notprovide strong corrosion resistance, but it may when alloyed with Niadvantageously shift the alloy potential in the noble, or positive,direction, and therefore may provide better protection for the Ag. Incertain examples, heat treatable (e.g., heat strengthened and/orthermally temperable) NiTi may provide improved performance,particularly with respect to durability and optics.

Furthermore, the above-mentioned materials for layers 8 and 10 may alsoprovide improved Ag dispersion in certain example embodiments. It isbelieved that providing better structural properties of the Ag may helpto achieve better optical properties such as dispersion. It further ispresently believed that the provision of a layer comprising NiTiOx nextto a layer comprising Ag may reduce agglomeration and early Ag filmcoalescence in certain instances.

FIG. 7 is based on FIG. 6. In FIG. 7, coating 50′ includes layers 6and/or 12 comprising NbZr, Zr, TiCr and/or TiNb, and layers 8 and/or 10comprising Ni-inclusive barrier layers.

FIG. 8 is also based on FIG. 6, and illustrates an exemplary exampleembodiment. In FIG. 8, coating 50″ comprises silicon nitride-baseddielectric layer 3 (optional dielectric layer 5 is omitted), first“barrier 2” layer 6 comprising NbZr, first “barrier 1” layer 8comprising C22, silver-based IR reflecting layer 9, second “barrier 1”layer 10 comprising C22, second “barrier 2” layer 12 comprising NbZr,and dielectric layer 13 comprising silicon nitride, which may also serveas a protective overcoat in some instances. However, in other exampleembodiments, a separate protective overcoat layer 16 may be provided. Incertain example embodiments, layer 16 may be zirconium-based, and may beof or include an oxide of zirconium and/or an alloy thereof. It also mayfurther include Al, Ti and/or Mo.

FIG. 9 is also similar to the FIG. 6 embodiment, but FIG. 9 is directedto a double-silver coating 60. FIG. 9 includes glass substrate 1,dielectric layer(s) 3 and/or 5, first “barrier 2” layer 6, first“barrier 1” layer 8, first IR reflecting layer 9 comprising Ag, second“barrier 1” layer 10, second “barrier 2” layer 12, third “barrier 1”layer 18, second IR reflecting layer 19 comprising silver, fourth“barrier 1” layer 20, fourth “barrier 2” layer 22, dielectric layer(s)13, and optional overcoat layer 16. In FIG. 9, “barrier 1” layers 8, 10,18, and/or 20 may be of or include any of the materials discussed hereinwith respect to “barrier 1” layers 8 and/or 10. Barrier layer 18 may,however, in certain example instances be of or include a differentmaterial as compared to barrier layers 8 and 10. “Barrier 2” layers 6,12, and 22 may be of or include any of the materials discussed hereinwith respect to “barrier 2” layers 6 and/or 12. Some, all, or none ofdielectric layers 3, 5 and/or 13 may be present according to differentexample embodiments. Dielectric layers 3, 5, and 13 may be of or includesilicon nitride, silicon oxide, silicon oxynitride, tin oxide, titaniumoxide, and/or any suitable dielectric material, In other exampleembodiments, a separate protective overcoat layer 16 may be provided. Incertain example embodiments, layer 16 may be zirconium-based, and may beof or include an oxide of zirconium and/or an alloy thereof, optionallyfurther including Al, Ti and/or Mo. Other dielectric layers may beprovided in other places in the coating in other examples.

FIG. 10 illustrates coating 50′″, which is similar to coating 50 shownin FIG. 6. However, coating 50″′ further includes dielectric layers 14and/or 15. In certain example embodiments, these dielectric layers maybe provided in between “Barrier 1” and “Barrier 2” under silver-basedlayer 9, and also may be provided in between “Barrier 2” and “Barrier 1”over silver-based layer 9. In certain example embodiments according toFIG. 10, “Barrier 2” layers 6 and 12 being sandwiched by dielectriclayers may further improve the chemical and/or mechanical durability ofthese layers and/or of the overall coating. Furthermore, the inclusionof dielectric layers 14 and/or 15 in a coating may advantageouslyfurther protect the silver-based layer from corrosion and/or scratching.In certain example embodiments, layers 14 and/or 15 may comprise siliconnitride, silicon oxide, silicon oxynitride, titanium oxide, tin oxide,and/or any other appropriate dielectric material. Furthermore, incertain example embodiments, layer 14 and/or 15 may be dense.

FIG. 11 illustrates coating 60′, which is similar to coating 60 shown inFIG. 9. However, coating 60′ also further includes dielectric layers 14′and/or 15. These layers are similar to layers 14 and 15 discussed above.Layers 14′ and 15′ also sandwich the “Barrier 2” layers that are closestto the glass substrate and farthest from the glass substrate,respectively. In the FIG. 11 embodiment, layers 6 and 22 are sandwichedby dielectric layers 3 and/or 5 and 14′, and 15′ and 13, respectively.

FIGS. 12 and 13 are cross-sectional views of coated articles accordingto example embodiments of this invention. In FIG. 12, the coated articleincludes glass substrate 1 (e.g., clear, green, bronze, or blue-greenglass substrate from about 1.0 to 10.0 mm thick, more preferably fromabout 1.0 mm to 6.0 mm thick), and a multi-layer coating 75 (or layersystem) provided on the substrate either directly or indirectly. FIG. 12includes dielectric layer(s) 3 and/or 5, a barrier layer 7 and/or 8,silver-based layer 9, barrier layer 10′, barrier layer 10″, and barrierlayer 24, as well as dielectric layer(s) 13, which may serve as anovercoat and/or top coat according to different example embodiments.Dielectric layers 3, 5, and 13 may be of or include silicon nitride,silicon oxide, silicon oxynitride, tin oxide, titanium oxide, and/or anysuitable dielectric material. Other dielectric layers may be provided inother places in the coating in other examples. In other exampleembodiments, a separate protective overcoat layer 16 may be provided. Incertain example embodiments, layer 16 may be zirconium-based, and may beof or include an oxide of zirconium and/or an alloy thereof, optionallyfurther including Al, Ti and/or Mo.

In FIG. 12, barrier layer 6, 7, and/or 8 may be of or include materialsdiscussed with respect to layer 7 of FIGS. 1-2 comprising a Ni-inclusiveternary alloy, “barrier 1” layer(s) 8 and/or 10, of or including Ni, Cr,Mo, and/or Ti, and/or “barrier 2” layer(s) 6 and/or 12, of or includingNb, Zr, Ti, Cr, and/or Nb. In some examples, only one of layers 6, 7,and 8 will be present in the FIG. 12 embodiment. However, in otherembodiments, more of the layers may be present.

FIG. 12 further includes barrier layer 10′, barrier layer 10″, andbarrier layer 16. In certain example embodiments, barrier layer 10′maybe Ni-inclusive such that it adheres well to the Ag-based layer 9.Particularly, in certain exemplary embodiments, layer 10′ may be of orinclude Ni and/or Ti, and/or an oxide thereof (e.g., Ni_(x)Ti_(y)O_(z)).Layer 10″ may be of or include Ni and/or Cr, and/or an oxide thereof.Layer 10″ may increase the mechanical durability of the overall coatingin certain example embodiments. Finally, layer 24 may be a “BarrierOxide” (BOx) layer in certain instances. In certain example embodiments,layer 24 may be of or include an oxide of Sn, TiCr, TiNb, NbZr, CrZr,NbMo, CrMo, WCr, WMo, WZr, WNb, WTi, CoMo, CoCr, CoZr, CoNb, and/orCoTi. In certain examples, the provision of barrier layer 16 may furtherimprove the durability of the coating.

FIG. 13 is based on FIG. 12, but includes a double IR reflecting layercoating 85. In certain example embodiments, the coated articleillustrated in FIG. 13 may be used as a monolithic window with a low-Ecoating with double IR reflecting layers. The coated article includesglass substrate 1 (e.g., clear, green, bronze, or blue-green glasssubstrate from about 1.0 to 0.0 mm thick, more preferably from about 1.0mm to 6.0 mm thick), and a multi-layer coating 85 (or layer system)provided on the substrate either directly or indirectly. FIG. 13includes dielectric layer(s) 3 and/or 5, a barrier layer 6, 7 and/or 8,silver-based layer 9, barrier layer 10, 11 and/or 12, Ag-based layer 19,barrier layer 10′, barrier layer 10″, and barrier layer 24, as well asdielectric layer(s) 13, which may serve as an overcoat and/or top coataccording to different example embodiments. In other exampleembodiments, a separate protective overcoat layer 16 may be provided. Incertain example embodiments, layer 16 may be zirconium-based, and may beof or include an oxide of zirconium and/or an alloy thereof, optionallyfurther including Al, Ti and/or Mo. Dielectric layers 3, 5, and 13 maybe of or include silicon nitride, silicon oxide, silicon oxynitride, tinoxide, titanium oxide, and/or any suitable dielectric material. Otherdielectric layers may be provided in other places in the coating inother examples.

In FIG. 13, barrier layer 6, 7 and/or 8 may be of or include materialsdiscussed with respect to layer 7 of FIGS. 1-2 comprising a Ni-inclusiveternary alloy, “barrier 1” layer(s) 8 and/or 10, of or including Ni, Cr,Mo, and/or Ti, and/or “barrier 2” layer(s) 6 and/or 12, of or includingNb, Zr, Ti, Cr, and/or Nb. In some examples, only one of layers 6, 7,and 8 will be present in the FIG. 13 embodiment. However, in otherembodiments, more of the layers may be present.

In FIG. 13, barrier layers 10′, 10″, and 24 may be of or include thematerials discussed herein with respect to layers 10′, 10″, and 24 inthe FIG. 12 embodiment.

In other example embodiments, the barrier layer materials above thesilver-based layer may be different from the barrier layer materialsprovided below the silver-based layer. All possible combinations for thebarrier layers mentioned herein may be used for any of the layer stacksshown in the figures and described herein.

In certain example embodiments, all binary, ternary, quaternary etc.alloys described herein may be sputtered from a single metallic and/orceramic target, or they may be co-sputtered from two or more differenttargets (metallic and/or ceramic) in different embodiments.

FIG. 14 is a cross-sectional view of a coated article according to anexample embodiment of this invention. In certain example embodiments,the coated article illustrated in FIG. 14 may be used as a monolithicwindow with a single functional layer. The coated article includes glasssubstrate 1 (e.g., clear, green, bronze, or blue-green glass substratefrom about 1.0 to 10.0 mm thick, more preferably from about 1.0 mm to6.0 mm thick), and a multi-layer coating 100 (or layer system) providedon the substrate either directly or indirectly. FIG. 14 includes glasssubstrate 1, optional dielectric layers 3 and/or 5, functional layer 9′comprising a NiCrMo-based alloy (e.g., C22, BC1, or B3), optionaldielectric layer 13, and optional overcoat layer 16. Other layers may beincluded in this coating. Layer 13 may be of or include silicon oxide,nitride, and/or oxynitride, and/or an oxide of titanium, tin, and/or thelike. In certain example embodiments, layer 16 may be zirconium-based,and may be of or include an oxide of zirconium and/or an alloy thereof,optionally further including Al, Ti and/or Mo.

FIG. 15 illustrates an exemplary embodiment based on the FIG. 14embodiment. FIG. 15 includes coating 100′. In FIG. 15, dielectric layer3 comprises silicon nitride, and dielectric layer 5 is excluded. It isnoted that any dielectric layer(s) described herein may be excludedaccording to different example embodiments. Moreover, these layers maybe split, or additional layers may be inserted, according to otherexample embodiments. Layer 9′ is the functional layer of the coating,and layer 9′ comprises C22 in the FIG. 15 embodiment. Dielectric layer13, which as indicated above may comprise more than one discrete layer,comprises silicon nitride, and layer 13′ comprises zirconium oxide. ZrOxinclusive layers may be provided as a protective overcoat layer indifferent embodiments of this invention, including those illustrated anddescribed above. In certain example embodiments, however, a layercomprising SixNy may be provided as an overcoat layer, e.g. as alludedto above.

FIG. 16 illustrates a further exemplary embodiment based on the FIG. 14embodiment. FIG. 16 is similar to FIG. 15, but FIG. 16 further includesbarrier layer 6′. Barrier layer 6′ may comprise a material discussed inthe FIGS. 6-9 embodiments with respect to the “barrier 2” layer. Thus,layer 6′ may serve as a barrier layer to functional layer 9′, and may beof or include NbZr, as shown in FIG. 16. In other example embodiments,layer 6′ may be of or include one or more of Nb, Zr, Ti and/or Cr.

The barrier layers discussed herein may be oxided and/or nitridedaccording to different example embodiments. These layers may bedeposited in the presence of oxygen and/or nitrogen, and/or may becomeoxided and/or nitrided during further processing steps such asdeposition of subsequent layers and/or heat treatment, according todifferent example embodiments.

Furthermore, the Ni-based ternary alloys discussed herein may bequaternary alloys or have even more than four materials than fouraccording to different example embodiments. In other words, althoughcertain example embodiments are described as “ternary alloys,” it willbe appreciated that such alloys may include three or more materials.

In further embodiments, a layer of or including NiCr and/or the targetused to sputter said layer may comprise NiCr in a ratio of 20:80, 40:60,60:40, or 80:20 (by weight). A layer of or including NiMo and/or thetarget used to sputter said layer may comprise NiMo in a ratio of 20:80,40:60, 60:40, or 80:20 (by weight). A layer of or including NbCr and/orthe target used to sputter said layer may comprise NbCr in a ratio of20:80, 40:60, 60:40, or 80:20 (by weight). A layer of or including NbZrand/or the target used to sputter said layer may comprise NbZr in aratio of 20:80, 40:60, 60:40, or 80:20 (by weight). Barrier layers asdescribed herein may further be of or include Haynes 214.

In certain example embodiments, the coated article illustrated in FIGS.1-16 may be used as a monolithic window with a low-E coating on surface1 and/or 2, where the low-E coating includes only a single IR reflectinglayer. However, in other example embodiments, the coated article in FIG.1 may comprise further layers. Furthermore, a coated article madeaccording to example embodiments described herein may be used in aninsulated glass unit (IOU), with the coating(s) on surface 1, 2, 3,and/or 4; in a laminated monolithic lite with the coating embedded in ordisposed on or against the interlayer on surfaces 2 and/or 3, or exposedon surface 4; in a laminated IGU, with a laminate outboard with thecoating embedded against the interlayer on surfaces 2 and/or 3, orexposed on surface 4; in a laminated IOU, with a laminated inboard withthe coated exposed on surfaces 3 and/or 6, or embedded on surfaces 4and/or 5, according to different example embodiments and applications.In other words, this coating may be used monolithically, or in IG unitscomprising two or more substrates, or more than once in a glass unit,and may be provided on any surface of the unit in different exampleembodiments. However, in other example embodiments, a coated article asdescribed herein may be used with any number of IR reflecting layers andmaybe combined with any number of other glass substrates to create alaminated and/or insulated glass unit. The coatings may also be used inconnection with IGU, VIG, automotive glass, and any other applications,according to different example embodiments.

Furthermore, the coatings in FIG. 1-16 as described herein may be usedon surface 1 for applications in which coatings are directly exposed tothe external atmosphere. In certain example embodiments, this mayinclude anti-condensation coatings. In other example embodiments, thismay include skylights, vehicle windows and/or windshields, IG units, VIGunits, refrigerator and/or freezer doors, and/or the like. The coatingsin FIG. 1-16 as described herein may also be applied to surface 4 ofdouble IG units, or surface 6 of triple JO units, to improve a window'sU-value. These coatings may also be used monolithically in applicationssuch as storm doors. In certain example embodiments, the coatings asdescribed herein advantageously proved excellent durability andstability, low haze, and smooth, easy to clean properties, in certainexample embodiments.

Other example embodiments for coatings described herein, particularlyfor monolithic coating applications, include anti-condensation coatings.Coatings as described herein may be used for surface 1 anti-condensationapplications. This may enable toe coating to be survivable in an outsideenvironment. In certain example embodiments, the coating may have a lowhemispherical emissivity such that the glass surface is more likely toretain heat from the interior area. This may advantageously reduce thepresence of condensation thereon.

Another example application for the coatings described herein includesthe use of an example coating or the materials disclosed herein tosurface 4 of an IG unit (e.g., the surface farthest from the sun),exposed to a building's interior. In these cases, the coating would beexposed to the atmosphere. In some cases, this may damage the Ag layerin the stack. However, by using a coating as described herein, thecoating including improved barrier materials and/or Ag alloys may haveimproved corrosion resistance, and better mechanical and/or chemicaldurability.

Although certain example embodiments have been described as relating tolow-E coatings, the various barrier layers described herein may be usedin connection with different types of coatings.

A coated article as described herein (e.g., see FIGS. 1-14) may or maynot be heat-treated (e.g., tempered) in certain example embodiments. Theterms “heat treatment” and “heat treating” as used herein mean heatingthe article to a temperature sufficient to achieve thermal temperingand/or heat strengthening of the glass inclusive article. Thisdefinition includes, for example, heating a coated article in an oven orfurnace at a temperature of at least about 550 degrees C., morepreferably at least about 580 degrees C., more preferably at least about600 degrees C., more preferably at least about 620 degrees C., and mostpreferably at least about 650 degrees C. for a sufficient period toallow tempering and/or heat strengthening. This may be for at leastabout two minutes, or up to about 10 minutes, in certain exampleembodiments.

As indicated above, certain example embodiments may include a low-Ecoating supported by a glass substrate. This coated article may be usedmonolithically or laminated to another glass or other substrate, Thecoated article also may be built into an insulated glass (IG) unit. IGunits generally comprise first and second substantially parallel spacedapart glass substrates. A seal is provided around the periphery of thesubstrates, and a gap (which may be at least partially filled with aninert gas such as Ar, Xe, Kr, and/or the like) is maintained between thesubstrates.

As alluded to above, the example materials disclosed herein may be usedin connection with low-E and/or anticondensation applications. Examplelow-E and/or anticondensation coatings are described in, for example,application Ser. Nos. 12/926,714; 12/923,082; 12/662,894; 12/659,196;12/385,234; 12/385,802; 12/461,792; 12/591,611; and 12/654,594, theentire contents of which are hereby incorporated herein by reference.Thus, for example, one or more of the barrier layer materials describedherein may replace or supplement one of more of the layers comprising Niand/or Cr in certain example embodiments. In certain exampleembodiments, one or more of the materials disclosed herein may replaceor supplement the functional IR reflecting (typically silver-based)layer or layers.

Some or all of the layers described herein may be disposed via sputterdepositing or any other suitable technique such as, for example, CVD,combustion deposition, etc.

As used herein, the terms “on,” “supported by,” and the like should notbe interpreted to mean that two elements are directly adjacent to oneanother unless explicitly stated. In other words, a first layer may besaid to be “on” or “supported by” a second layer, even if there are oneor more layers therebetween.

While the invention has been described in connection with what ispresently considered to be the most practical and preferred embodiment,it is to be understood that the invention is not to be limited to thedisclosed embodiment, but on the contrary, is intended to cover variousmodifications and equivalent arrangements included within the spirit andscope of the appended claims.

What is claimed is:
 1. A method of making a coated article comprising acoating supported by a glass substrate, the method comprising: disposinga first dielectric layer on the substrate; disposing an IR reflectinglayer comprising 63-67 wt. % Ni, 1-2 wt. % Cr, 25-30 wt. % Mo, 1-5 wt. %W, and 1-5 wt. % Co over and contacting the first dielectric layer; anddisposing a second dielectric layer over and contacting the IRreflecting layer.
 2. The method of claim 1, wherein the first and seconddielectric layers comprise silicon nitride.
 3. The method of claim 1,further comprising disposing a protective overcoat comprising an oxideof zirconium as an outermost layer of the coating.
 4. The method ofclaim 1, further comprising providing a barrier layer between the IRreflecting layer and the second dielectric layer.
 5. The method of claim4, wherein the barrier layer comprises NbZr.
 6. The method of claim 1,wherein the first and second dielectric layers comprise silicon nitride,and wherein the coating further comprises a barrier layer comprisingNbZr provided between the IR reflecting layer and the second dielectriclayer, and a protective overcoat comprising an oxide of zirconium as theoutermost layer of the coating.
 7. The method of claim 1, wherein thecoating comprises only one IR reflecting layer, and wherein the coatedarticle is used monolithically.
 8. A method of making an insulated glass(IG) unit, the method comprising: providing the coated article of claim1; and providing a second substrate; positioning the coated articlerelative to the second substrate so that the coating on the coatedarticle is located on surface 1 or on surface 4 of the IG unit in makingthe IG unit.
 9. A method of making an insulated glass (IG) unit, themethod comprising: providing first and second coated articles accordingof claim 1; and positioning the first and second coated article relativeto one another so that the coating of the first coated article is on anexterior surface of the IG unit adapted to face a building exterior. 10.The method of claim 1, wherein the coating comprises only one IRreflecting layer comprising 63-67 wt. % Ni, 1-2 wt. % Cr, 25-30 wt. %Mo, 1-5 wt. % W, and 1-5 wt. % Co.
 11. The method of claim 1, whereinthe coating comprises only one IR reflecting layer.
 12. The method ofclaim 1, wherein the IR reflecting layer comprise about 3% (wt. %) W.13. The method of claim 1, wherein the IR reflecting layer compriseabout 3% (wt. %) Co.
 14. The method of claim 1, wherein the IRreflecting layer comprise about 65% (wt. %) Ni.
 15. The method of claim1, wherein the IR reflecting layer comprise about 28.5% (wt. %) Mo.